N-formyl n&#39;-carbamyl phenylene diamines and preparation thereof



United States Patent N-FORMYL N-CARBAMYL PHENYLENE DI- AMINES AND PREPARATION THEREOF Saul R. Buc, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. ApplicationApril 27, 1953, Serial No. 351,490

18 Claims. (Cl. 260-553) This invention relates to the preparation of new phenylen'ediamine derivatives, and more particularly to the preparation of asymmetrically substituted phenylenediamine derivatives wherein one amino group is alkylated and formylated and the second amino group is converted to form a substituted urea type compound.

One object of my invention is to provide a new class of chemical compounds derived from phenylenediamines and methods of making same.

Another object of my invention is to provide new chemical compounds derived from meta-phenylenediamine and methods of making same.

Still another object of my invention is to provide .new chemical compounds derived from para-phenylenediamine and methods of making same.

Other objects will become apparent hereinafter.

The chemical compounds contemplated herein have the following structural formula:

Noomn werein R represents an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, etc., and R represents hydrogen or any of the groups which R may represent.

In accordance with my invention the chemical compounds encompassed herein are, prepared from compounds of the following structural formula:

r R v wherein R and R may-.be any of the-groups defined above and X may be hydrogen or''CHO,"which compounds are first treated with hydrochloric acid to form the corresponding hydrochloride salt having the formula:"

' pounds encompassed by the generic formula given above.

T 2,728,794 Patented Dec. 27, 1955 Serial No. 224,444, filed May 3, 1951, now U. S. Patent 2,647,815. The symmetrical dialkyl, diformyl metaand para-phenylenediamines may also be prepared from resorcinol and hydroquinone by the Biicherer reaction with subsequent formylation. The extension of the Biicherer reaction to hydroquinone to produce dialkylated phenylenediamines is described in copending application Serial No. 265,042, filed January 4, 1952.

It is also within the scope of the present invention to prepare compositions containing a mixture of com- Said mixtures may contain not only a plurality of dialkylated derivatives wherein the alkyl group on the same nucleus are similar but may also contain dialkylated derivatives having different alkyl groups on the same nucleus. Such mixtures of the diformyl precursor compounds are described in the aforementioned applications. No attempt has been made to isolate the individual components of said mixture since the mixtures are valuable compositions in themselves.

The compounds and compositions of this invention are valuable intermediates in the preparation of other organic compounds. The compounds and compositions are particularly valuable as solubilizing agents for ionic compounds in polar solvents. Specificaly, the compounds of my invention are extremely effective for promoting the solubilization of the alkali metal salts of the sulfuric acid esters of the leuco form of vat dyestuffs in aqueous mediums, and particularly in aqueous printing paste formulations. This property of the instant compounds is extremely valuable since one of the major problems one is faced with in vat dyeing is to produce a uniform, level, nonspecky dyed product. To effect this, it is necessary to have the dyestulf in as fine a state of sub-division as possible and preferably in solution. The new compounds and compositions of this invention enhance the solubility of the sulfuric acid esters of vat dye-stuffs in aqueous mediums, thereby leading to level, non-specky dyeings.

The compounds and compositions of the present invention include the following:

III-CHO CH3 N,N'-dimethyl, N-formyl N-carbamy1 m-phenylenediamine C2115 liq-CHO N,N'-diethyl, N-formyl N'-carbamy1 p-phenylene-diamine oaHs N-CHO.

N,N-diethyl, N-formyl N-earbamyl m'phenyIene-diamine 3 4 CH: EXAMPLE 1 bl' -OHO N',N-dimethyl; N-formyl', Al'warbamyl m-phenylenediamme A sample of N,N-dirnethyl, N,N-diformyl m-phenylenediamine, described in application Serial No. 224,444, CONE is refluxed with exactly one equivalent of HCl as a 2 solution until no precipitate is. formed on cooling. The

H3 10 resulting solution of the monohydrochloride N,N-dimethyl, N-formyl N'-carbamyl ppl1cny1eneclia:nino

(llHa (3H3 N-OHO 1\|IOHO l -Il|l'+-CH;CT-

l t NHO ONHZ is cooled with ice and treated with a slight excess of 5 N-methyl, y N-Carbamy1p-pllenylene-dlamme potassium cyanate. The product which has the formula C2115 CH3, N OH I i-CHO I -NO ONHV l NHCONH H3 N-ethyl N-form 1 N'-carbamy1 p-phenylene-diamine y precipitates and 1S filtered off, washed, and dried.

EXAMPLE 2 N,N-diethyl, N-formyl, N-carbamyl p-phenylenediamine A sample of N,N'-diethyl, N;N"-diformyl, p-phenylenediamine, described in application Serial No. 224,444 is A 0 ONE treated in the identical manner set forth in Example 1.

40 The product has the formula: Ha N-ethyl, N"-methy1, N-formyl, N'-cai'bamyl p-phenylenediamine C7H5 CH3 NCHO l 1 |I-OHO l I-OO-NH2 I l-CONE: 51115 EXAMPLE 3 N-methyl, N-ethyl N-formyl, N-carbamyl p-phenylenediamine CH N ,N '-diethyl, N -f0rmyl, N "-carbamyl m-phenylenediamine 3 .1l1' ONE A sample of N,N'-di'ethyl, N;N-diformyl m-phenylenediarnine, descrihed" in. application Serial" No. 224,444, is-

treated in the identical manner set forth in. Example 1.

The product has the formula: N-OHO 02H F A N-CHO N-methyl, N-ethy1, N-carbamyl N-f0rmy1 in-phenylenediamine I l IQ-CONE N-C'ONH:

LL 7O EXAMPLE14 H3 N',N'-dimethyl; N-formyl, N -carbamyl p-phenylenedi- N-ethyl, N'-metl1y1, N-carbamyl N-formy1 m-phenylenediamine amine The following examples will serve to illustrate further A sampleof NN"-dimethyl; N,N"-diform ll p-phenyl'enethe manner of practicing my invention. diamine, described in application Serial No. 224,444;

is treated in the identical manner set forth in Example 1. The product has the formula r IIP-CHO I N-CONHz EXAMPLE 5 N -methyl, N -f0rmyl, N -carbamyl, p-phenylenediamine A sample of p-amino, N-methyl formanilide, as described in application Serial No. 224,444, is dissolved in a slight excess of hydrochloric acid and treated with a slight excess of potassium cyanate in the presence of ice. The product crystallized at once as it filtered, washed, and dried. The product has the formula HN-OONH:

EXAMPLE 6 N-ezhyl, N-formyl, N'-carbamyl, p-phenylenediamine This compound is prepared identically as the one of Example 5, but starting with the corresponding ethyl derivative. The product has the formula:

Hi l-O ONH2 EXAMPLE 7 A sample of a mixture of N,N-dimethyl, N,N'-diformyl p-phenylenediamine, N,N'-diethyl, N,N-diformylp-phenylenediamine and N-methyl, N'-ethyl, N,N'-diformyl-p-phenylenediamine, wherein the methyl and ethyl groups are in the ratio of 1:3 (described in application Serial No. 224,444) is treated as in Example 1. The resulting composition comprises a mixture of the compounds of Examples 2 and 4 and additionally the compounds N-ethyl, N'-methyl, N-forrnyl, N'-carbamyl pphenylenediamine and N-methyl, N'-ethyl, N-formyl, N- earbamyl-p-phenylenediamine wherein the methyl to ethyl groups are in the ratio of 1:3.

I claim: 1. Compounds of the formula R-ETCHO lTl'CONHz wherein the relationship of the nitrogen atoms is selected from the group of positions consisting of meta and para, wherein R is a lower alkyl radical and R is a member selected from the group consisting of hydrogen and lower alkyl radicals.

. 6 2. Compounds of the formula RN-CHO NOONH2 wherein R is a lower alkyl radical and R' is a member selected from the group consisting of hydrogen and lower alkyl radicals.

3. Compounds as defined in claim 2 wherein R and R are-alkyl radicals.

4. Compounds as defined in claim 2 wherein R alkyl radical and R is hydrogen.

5. Compounds of the formula is an and I l-CONE:

2H5 9. The compound N,N-diethyl, N-formyl, N'-carbamyl m-phenylenediamine having the formula:

N-CHO IFTCONH2 02H; 10. The compound N,N'-dimethyl, N-formyl, N'-carbamyl m-phenylenediamine having the formula:

l i v-orro N-C ONH:

11. The compound N,N'-dimethyl, N-formyl, N'-carbamyl p-phenylenediamine having the formula:

CllHa IYI-CHO l N-CONH:

12. The compound N-methyl, N-formyl, N-carbamyl p-phenylenediamine having the formula (1H3 III-43110 13. The mixture of N,N'-diethyl, N-formyl, N-carbamyl p-phenylenediamine, N,N-dimethyl,, N-formyl, N-carbamyl p-phenylenediamine, N-ethyl, N-methyl, N-formyl, N'-carbarnyl p-phenylenediamine, and N- methyl, N'-ethyl, N-forrnyl, N-carbamyl p-phenylenediamine wherein the methyl to ethyl groups are in the ratio of 1:3.

14. A process for preparingcompounds of the formula NC ONH:

wherein the relationship of the nitrogen atoms is selected from the group of positions consisting of meta and para, wherein R is a lower or alkyl radical and R is a member selected from the group consisting of hydrogen and lower alkyl radicals, which comprises first treating compounds ofthe formula wherein R is a lower alkyl radical and R is a member selected from the group consisting of hydrogen and lower alkyl radicals and X is a member selected from the group consisting of hydrogen and -CHO, with hydrochloric acid to form the corresponding hydrochloride salt and then treating with potassium cyanate.

15. A process for preparing compounds of the formula R-lTP-C HO NCONHa 8 wherein the. relationship of the nitrogen atoms is. selected from the group of positions consisting of meta and para,. wherein R is a lower alkyl radical and R" is a member selected from the group consisting of hydrogen and lower alkyl radicals, which comprises first treating compounds of the formula wherein R is a lower alkyl radical, R is a member selected from the group consisting of hydrogen and lower alkyl radicals and X is a member selected from the group consisting of hydrogen and CI-IO, with hydrochloric acid to form the corresponding hydrochloride salt, cooling said salt in solution, treating said solution with a slight excess of potassium cyanate and isolating the resulting amide.

16. The process for preparing N,N-diethyl, N-formyl, N-carbamyl p-phenylenediamine which comprises refluxing N,N"-diethyl, N,N-diformyl p-phenylenediamine: with about one equivalent of a solution of hydrochloric acid until no precipitate is formed on cooling, cooling the resulting solution, adding a slight excess of potassium cyanate and isolating the resulting precipitate of N,N-diethyl, N-formyl, N-carbamyl p-phenylenediarnine.

17. The process for preparing N,N-dimethyl, N- formyl, N-carbamyl p-phenylenediamine which comprises refluxing N,N -dimethyl, N,N-'-dif'ormyl p-phenylenediamine with about one equivalent of a solution of hydrochloric acid until no precipitate is formed on cooling, cooling the resulting solution, adding a slight excess of potassium cyanate and isolating the resulting precipitate of N,N -dimethyl, N-formyl, N-carbamyl p-phenylenediamine.

1.8. The process for preparing N -methyl, N-formyl, N- carbamyl p-phenyl'enediamine which comprises dissolving p-amino, N-methyl formanilide in hydrochloric acid, treating with a slight excess of potassium cyanate at a temperature of about 0 (3., and isolating the resulting precipitate of N-methyl, N-formyl, N-carbamyl p-phenylenediamine.

No references cited. 

1. COMPOUND OF THE FORMULA 